eXPRESS Polymer Letters Vol.10, No.

11 (2016) 927940
Available online at www.expresspolymlett.com
DOI: 10.3144/expresspolymlett.2016.86

Bio-based polyurethane prepared from Kraft lignin and

modified castor oil
L. B. Tavares, C. V. Boas, G. R. Schleder, A. M. Nacas, D. S. Rosa, D. J. Santos*

Centro de Engenharia, Modelagem e Cincias Sociais Aplicadas, UFABC, Santo Andr, 09210-580 So Paulo, Brazil

Received 24 April 2016; accepted in revised form 26 June 2016

Abstract. Current challenges highlight the need for polymer research using renewable natural sources as a substitute for pe-
troleum-based polymers. The use of polyols obtained from renewable sources combined with the reuse of industrial residues
such as lignin is an important agent in this process. Different compositions of polyurethane-type materials were prepared by
combining technical Kraft lignin (TKL) with castor oil (CO) or modified castor oil (MCO1 and MCO2) to increase their re-
activity towards diphenylmethane diisocyanate (MDI). The results indicate that lignin increases the glass transition temper-
ature, the crosslinking density and improves the ultimate stress especially for those prepared from MCO2 and 30% lignin
content from 8.2 MPa (lignin free) to 23.5 MPa. Scanning electron microscopy (SEM) micrographs of rupture surface after
uniaxial tensile tests show ductile-to-brittle transition. The results show the possibility to develop polyurethane-type materials,
varying technical grade Kraft lignin content, which cover a wide range of mechanical properties (from large elastic/low
Young modulus to brittle/high Young modulus polyurethanes).

Keywords: mechanical properties, reinforcements, Kraft lignin, lignopolyurethane materials, modified castor oil

1. Introduction Castor oil is a major candidate in these replacement

Increasing concerns about depletion of petroleum-
based resources and environmental problems caused
by petroleum-based materials have led to consider-
able efforts to develop materials based on renewable
resources such as vegetable oils, cellulose, lignin,
starch, etc. [1]. The use of renewable raw materials
can significantly contribute to sustainable develop-
ment due to degradability and low toxicity of the re-
sulting products. Conventional polyurethanes (PU)
are usually synthesized by a polyaddition reaction be-
tween polyols, which are petrochemical in origin and
polyisocyanate, which forms urethane linkages [2] re-
sulting in a crosslinked polymer. Nevertheless, poly-
urethanes can be obtained by using renewable sources
such as vegetable oils and can replace fossil fuel-de-
rived oligomers partially or totally.
efforts due to its inherent advantages over other veg-
etable oils [3]. Besides its renewability, low cost and
easy availability in large quantities, castor oil is not
edible, and does not compete with food, and has free
secondary hydroxyl groups. Approximately 90% of
fatty acids in castor oil are ricinoleic acid (C18:1),
which have a hydroxyl functional group at the 12th
carbon. This provides a hydroxyl value of between
160 and 180 mg KOH g1 [4, 5]. However, this low
hydroxyl value along with the presence of secondary
hydroxyls results in low functionality and low reac-
tivity [6, 7], leading to low crosslinking density, which
consequently produces semi-flexible and semi-rigid
materials among other limitations [8]. Sharma et al.
[7] investigated flexible polyurethane foams synthe-
sized partially and completely from castor oil. They
showed that foams made from 100% of castor oil

*Corresponding
author, e-mail: demetrio.santos@ufabc.edu.br
BME-PT

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 Tavares et al. eXPRESS Polymer Letters Vol.10, No.11 (2016) 927940
were unstable and collapsed indicating the inferior
reactivity of castor oil with isocyanate. The modifi-
cation of castor oil increases its hydroxyl value and
hard segment composition to improve the rigidity,
physical and mechanical properties and crosslinking
density of the final PU products [9]. Nevertheless, the
hydroxyl value of modified castor oil is limited.
A renewable and promising source for sustainable
chemicals and bio-based polymeric materials is lignin.
Its phenylpropanoic structure and high content of di-
verse functional groups (such as phenolic and aliphat-
ic hydroxyls, carbonyls, carboxyls) allow it to be
used as an alternative for polymer development es-
pecially in the substitution of petroleum-based poly-
ols in polyurethane synthesis. Many tons of lignin are
generated as by-products of industrial processes such
as pulp and paper. Most of the lignin extracted from
pulp and paper operations is burned during pulp-spent
liquor treatment. This offers energy recovery and re-
generation of pulping chemicals with less than 2%
recovered for utilization as a chemical product [10].
However, the amount of lignin produced exceeds the
requirements for energy generation. The type of pulp-
ing process determines the type of lignin industrially
available because it unavoidably modifies the lignin
structure from that in the original feedstock. To in-
crease the potential applications of lignin in poly-
meric materials, some chemical modifications have
been developed [11, 12], but these add stages to the
process and/or raise their costs considerably. There-
fore, the direct use of industrial lignin is the most fa-
vorable option because it is a relatively cheap raw
material. Unmodified lignin has poor stability [13]
and difficult melt processing [14], which make its di-
rect use uncompetitive. However, many studies have
focused on the incorporation of lignin in polymer
materials by blending it with synthetic or other bio-
based polymers [1517].
Current studies have shown increasing interest in di-
versifying the sources of the hydroxyl groups. Mo-
hamed et al. [18] successfully synthetized an eco-
friendly waterborne polyurethane dispersion, from
castor oil and aromatic polyamide sulfone, via copoly-
merization reaction. Alternatively, combining lignin
and castor oil as polyols for polyurethanic materials
is promising. This can produce diversified materials
with varied properties and applications. de Oliveira
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et al. [19] characterized polyurethanic materials
based on sulfonated lignin (unmodified and modified
by oxypropylation) and castor oil. The DMA results
pointed out that the glass transition temperature (Tg)
of the samples increased and thus the degree of cross-
linking with the increase of hydroxyl groups derived
from different combinations of sulfonated lignin/
sulfonated ligin oxypropylated/castor oil as polyols.
Cinelli et al. [20] characterized flexible polyure-
thanes foams from liquefied lignin and two different
chain extenders: castor oil and poly(propylene gly-
col) (PPG). The single use of unmodified or modified
castor oil as a polyol is already consolidated [3, 21].
Modified lignins have also been studied for this ap-
plication [22, 23]. However, the combination of mod-
ified castor oil (MCO) and unmodified industrial
lignin shows an interesting opportunity for renewable
and low cost polyols for preparation of PU.
The aim of this work is to develop and to character-
ize polyurethane obtained from renewable sources by
using polyols including modified castor oil and un-
modified paper and pulp residue lignin. The influ-
ences of the basic chemistry reactions formed from
different combinations were investigated. Fourier
transform infrared spectroscopy (FTIR) was used to
identify functional groups of the polymers. The ther-
mal and mechanical properties were studied using
thermogravimetric analysis (TGA), dynamic mechan-
ical analysis (DMA) and tensile property measure-
ments. Our research efforts focused on the develop-
ment of novel 100% renewable polyols able to syn-
thetize polyurethanes with a wide range of glass tran-
sition temperature (Tg) and mechanical properties.
The wide range of lignin-containing polyurethane
mechanical properties can make it suitable for the re-
placement of petroleum-based PU on several appli-
cations.
2. Experimental section
2.1. Materials
Technical Kraft lignin (TKL) was obtained as a
byproduct of pulp and paper production. It was kind-
ly supplied by Suzano Papel e Celulose (Suzano, SP,
Brazil) with the following characteristics: brown
color, Mw = 3388 gmol1 (obtained by gel perme-
ation chromatography) pH 8.1, solid content = 92.5%,
ashes = 10% and total hydroxyl index equivalent to
 Tavares et al. eXPRESS Polymer Letters Vol.10, No.11 (2016) 927940
Figure 1. Schematic drawing of castor oil modification reaction
243 mg KOH g1 (determined by 31P nuclear mag-
netic resonance). The TKL was dried at 80 C for 6 h
before polyol preparation.
Castor oil (CO) and two types of modified castor oil
(MCO1 and MCO2) were provided by CPA Brazil
(Diadema, SP, Brazil) with a hydroxyl index of 159,
237 and 286 mg KOH g1 and acid index of 0.95, 3.87
and 4.25 mg KOH g1, respectively (determined by
titration). MCO1 and MCO2 were synthetized using
a stainless steel industrial reaction kettle equipped
with mechanical stirring, temperature monitoring,
cooling control system and N2 inlet. Castor oil was
modified by reacting with glycerol and Ca(OH)2
(1% of reactant total mass) at 230 C for 8 h. Varying
castor oil/glycerol ratios gave modified castor oils
with different hydroxyl index. The reaction scheme
of castor oil modification is shown in Figure 1.
Diphenylmethane diisocyanate (MDI) was acquired
for polyurethane preparation from Kalium Chemical
(So Paulo, SP, Brazil). It contained 30 and 32%
(minimum and maximum) NCO group values.
2.2. Polyurethane preparation
Natural renewable source lignin-containing polyols
were obtained by adding 10, 20 or 30 wt% of tech-
nical Kraft lignin (TKL) with castor oil (CO) or with
modified castor oils (MCO1 or MCO2). Lignin-con-
taining polyols were obtained by stirring 50 g of CO,
MCO1 or MCO2 and the respective lignin weight
ratios. Polyol preparation was carried out under air at
room temperature, for 10 min at 80 rpm in a 200 mL
Table 1. Nomenclature and compositions of developed polyols according to TKL and oil wt%
PU-CO PU-CO/L10
TKL [wt%] 0 10
CO [wt%] 100 90
PU-MCO1 PU-MCO1/L10
TKL [wt%] 0 10
MCO1 [wt%] 100 90
PU-MCO2 PU-MCO2/L10
TKL [wt%] 0 10
MCO2 [wt%] 100 90
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beaker. Polyurethanes (PU-CO, PU-MCO1 and PU-
MCO2) were prepared by mechanically mixing MDI
and the natural renewable source lignin-containing
polyols (NCO/OH equivalent molar ratio of 1.2) for
2 min at 20 rpm in a 200 mL beaker [19]. Polyol com-
positions are presented in Table 1.
The mixed polyurethane was poured into the cavities
of an open silicon mold, with cavity dimensions ac-
cording to ASTM D638-10 specimens Type I. The
cure was carried out at room temperature for 7 days.
Figure 2 shows representative reaction schemes be-
tween TKL/MDI/modified castor oil, which eluci-
dates the urethane group formation and consequent
polymeric structure.
2.3. Characterizations
2.3.1. Fourier transform infrared spectroscopy
(FTIR)
The spectroscopic measurements in the infrared re-
gions (FTIR) were performed in a Thermo Nicolet
Nexus 4700 spectrometer in transmittance mode; 10
scans were performed from 4000500 cm1 with a
resolution of 4 cm1 in each sample.
2.3.2 Thermogravimetric analysis (TG)
Thermogravimetric analysis (TG) was carried out
using Netzsch equipment model STA 449F3. The
samples (11.0 mg) were heated from 25 to 800 C
under nitrogen atmosphere and 50 mLmin1 flow
and a heating rate of 10 Cmin1.
PU-CO/L20 PU-CO/L30
20 30
80 70
PU-MCO1/L20 PU-MCO1/L30
20 30
80 70
PU-MCO2/L20 PU-MCO2/L30
20 30
80 70
 Tavares et al. eXPRESS Polymer Letters Vol.10, No.11 (2016) 927940

Figure 2. Schematic drawing of polyurethane groups formation from TKL/MDI/MCO reaction

2.3.3. Dynamic mechanical analysis (DMA)
Glass transition temperature (Tg) of renewable poly-
ol based polyurethanes was investigated by DMA
using a thermal analyzer model Pyris Diamond,
Perkin Elmer. Measurements were carried out in flex-
ural mode (single cantilever) with a temperature range
from 50 to 150 C, frequency of 1 Hz, oscillation
amplitude of 10 mm and heating rate of 2 Cmin1.
The dimension of specimens was 30 mm12 mm
2 mm, which were obtained by casting PU into the
cavities of an open silicon mold. Storage modulus at
rubbery plateau (ER) was used to calculate cross-
linking density.
2.3.4. Mechanical properties
The mechanical properties (5 specimens for each con-
dition) were tested according to ASTM D638 with
Type I test specimens using an Instron universal test-
ing machine model 5569 (CECS, Federal University
of ABC, Santo Andr, SP, Brazil) with a crosshead
speed of 50 mmmin1 and a non-contact extensome-
ter (Instron SVE). Type I test specimens presented
following dimensions: overall length (165 mm), width
of narrow section (13 mm), overall thickness (5 mm)
and gage length (50 mm).
2.3.5. Scanning electron microscopy (SEM)
After mechanical testing, SEM was used to observe
the cross sectional morphology of the fractured sur-
faces of the samples using a Jeol 6460LV scanning
electron microscope with an electron beam at an ac-
celerating voltage of 25 kV. The samples were set on
the SEM sample holder and sputter coated with a
thin layer of gold.

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3. Results and discussion
3.1. Fourier transform infrared spectroscopy
(FTIR)
Figure 3 shows the FTIR analysis for CO, MCO1
and MCO2 oils. All spectra present the characteristic
peak at 3400 cm1. This corresponds to the hydroxyl
group. MCO1 and MCO2 show increase in this band
intensity (Figure 3b), which is related to hydroxyl
value increasing after modification. Other character-
istic absorption bands are observed at 2920 cm1
(methyl), 2850 cm1 (methylene), 1740 cm1 (esters)
and 1161 cm1 (COC) [23-26].
Figure 4 compares the FTIR spectra of PU-CO, PU-
MCO1 and PU-MCO2. A characteristic band of ure-
thane stretching at 3330 cm1 is present on all sam-
ples, which corresponds to hydrogen bonded NH
group in disordered form [19, 24]. The increasing in-
tensity of this band (Figure 4b) shows the increased
amount of urethane groups for PU-MCO1 and PU-
MCO2, which might be associated with reaction of
NCO with increased hydroxyl level of MCO1 and
MCO2. The absence of NCO stretching at 2260 cm1
indicates that the isocyanate groups have been entirely
reacted [19, 24, 27]. Other main absorption bands
confirm polyurethane formation including absorp-
tions in the region between 17041709 cm1 (car-
bonyl group hydrogen bonding to the urethane group)
and 1215 cm1 (urethane linkages) [19, 23, 27].
Figure 5 shows the FTIR spectra of lignin-containing
polyurethanes (varying the TKL wt% into the poly-
urethanes) and of TKL (Figure 5b, 5d and 5f). The
band at 3425 cm1, TKL spectrum (Figure 5b, 5d and
5f), is characteristic of its aromatic and aliphatic OH
bond stretching [15, 28, 29]. The presence of lignin
in polyurethane resulted into the formation of a wider
band in the 33303425 cm1 region due to merging
of the bonded NH band (3330 cm1) with lignin OH
bond stretching (3425 cm1) [27]. It can be observed
in parts b, d and f of Figure 5 that the intensity of the
merged region increases with the increasing of lignin
quantity for all samples.

Figure 3. FTIR spectra of vegetable oils (CO, MCO1 and MCO2) (a) from 3700 to 600 cm1 and (b) from 3700 to 3000 cm1

Figure 4. FTIR spectra of PU-CO, PU-MCO1 and PU-MCO2 (a) from 3700 to 600 cm1 and (b) from 3700 to 3000 cm1

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Figure 5. FTIR spectra of PU-CO/lignin compositions (a) from 3700 to 600 cm1, (b) PU-CO/lignin and lignin (TKL) from
3700 to 3000 cm1; of PU-MCO1/lignin compositions, (c) from 3700 to 600 cm1, (d) PU-CO1/lignin and lignin
(TKL) from 3700 to 3000 cm1; and PU-MCO2/lignin (e) from 3700 to 600 cm1, (f) PU-CO2/lignin and lignin
(TKL) from 3700 to 3000 cm1

As can be seen in Figures 5a, 5c and 5e the spectra
of lignin-containing polyurethanes show that as the
lignin content increases, the peak of the carbonyl
stretching vibration (around 1700 cm1) gradually
shifted to higher wavenumbers. Carbonyl bands of
polyurethane can be divided on three main regions:
the hydrogen bonded carbonyl in ordered crystalline
domains at 17001709 cm1 [19, 24, 27], the hydro-
gen bonded carbonyl in disordered amorphous con-
formations at 17141720 cm1 [19, 30] and the free
carbonyl groups (non bonded) at 17311745 cm1
[23, 31]. The carbonyl band shifting indicates that the
presence of lignin induces the change from a hydro-
gen bonded ordered crystalline domain (PU-CO, PU-
MCO1 and PU-MCO2) to a disordered amorphous
conformation and to the formation of free carbonyl
groups (PU-CO/lignin, PU-MCO1/lignin and PU-
MCO2/lignin) [27]. The absence of NCO stretching
at 2260 cm1 in all lignin-containing polyurethane
spectra indicates that the isocyanate groups have
been entirely reacted [19, 24, 27].
3.2. Thermogravimetric analysis (TGA)
The TGA and derivative TG curves for castor oil-
based PU and castor oil/lignin-based PU are present-
ed in Figures 6 and 7. The stability of the PU is related
to the hard segment nature (rigid aromatic ring of
MDI and TKL), soft segment (introduced by flexible
chains of castor oil) and the molar ratio of the hard
segment to soft segment [32]. In general, the thermal
degradation of polyurethane occurs in a two to three
steps, and the composition of the decomposed prod-
ucts depends on the structure of the PU material [33].

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Figure 6. (a) TGA curves of PU-CO, PU-MCO1 and PU-MCO2 and (b) DTG curves of PU-CO, PU-MCO1 and PU-MCO2

Figure 7. (a) TGA curves of PU-CO and PU-CO/lignin, (b) DTG curves of PU-CO and PU-CO/lignin, (c) TGA curves of
PU-MCO1 and PU-MCO1/lignin, (d) DTG curves of PU-MCO1 and PU-MCO1/lignin, (e) TGA curves of PU-
MCO2 and PU-MCO2/lignin and (f) DTG curves of PU-MCO2 and PU-MCO2/lignin compositions

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A first step decomposition is observed around 270 C Table 2. Thermogravimetric parameters of PU-CO/lignin,
and is related to the thermal decomposition of unsta- PU-MCO1/lignin and PU-MCO2/lignin
ble urethane bonds [27]. The second step occurs Tonset T50% Toffset Char residue
[C] [C] [C] [%]
above 320 C. The mass loss occurs at a fast rate in PU-CO 290.7 421.5 484.6 11.2
this step. It is associated to the soft segment and de- PU-CO/L10 287.7 434.8 485.9 17.0
pends on its structure and three-dimensional arrange- PU-CO/L20 284.2 438.1 480.9 22.2
ment [33]. The third one is above 380 C and is also PU-CO/L30 282.3 437.2 478.8 24.6
related to other remaining structures formed after the PU-MCO1 267.1 453.7 486.3 13.3
PU-MCO1/L10 265.6 452.6 487.9 19.5
second decomposition, diisocyanate and lignin aro-
PU-MCO1/L20 264.8 440.9 486.3 26.1
matic rings [1, 25, 34]. PU-MCO1/L30 264.3 444.9 477.8 26.5
Figure 6 shows the TGA and derivative curves of PU-MCO2 267.3 441.8 492.6 13.9
PU-CO, PU-MCO1 and PU-MCO2, respectively. The PU-MCO2/L10 263.6 440.9 488.7 18.4
PU-MCO2 and PU-MCO1 showed lower degrada- PU-MCO2/L20 258.0 429.0 480.3 20.3
PU-MCO2/L30 259.9 441.5 485.5 24.6
tion temperature for first step decomposition (max-
imum peaks at 289.3 and 294.2 C, respectively) and
presented higher mass loss compared to PU-CO mogravimetric parameters, including initial decom-
(320.0C) due to increasing urethane groups that were position temperature for degradation step (Tonset),
improved by castor oil modification. The second step final decomposition temperature for degradation step
decomposition may correspond to the chain scission (Toffset), temperature for 50% mass loss (T50%) and
of CO (PU-CO 393.6C, PU-MCO1 372.3 C, and % mass of remaining char at 750 C.
PU-MCO2 370.9 C), the soft polyurethane segment,
also observed by Hablot et al. [35]. In the third step 3.3. Dynamic mechanical analysis (DMA)
of decomposition, DTG peaks are shown at 448.5 C The evolution of tan as function of temperature is
for PU-CO, 457.1 C for PU-MCO1, and 459.4 C presented in Figure 8 and might be attributed to the
for PU-MCO2. glass transition temperature (Tg) [23]. A wide Tg range
Figure 7 shows TGA and DTG curves of PU-CO/ might be obtained for polyurethanes, which is de-
lignin, PU-MCO1/lignin and PU-MCO2/lignin com- pendent on polymer segment, hard and soft nature,
positions. The presence of lignin for all conditions and composition [19].
decreased the onset of thermal decomposition. The Figure 8a shows the glass transition temperature of
degradation onset in the 250290 C temperature PU-CO and PU-CO/lignin conditions. Tan values
range corresponds to the decomposition of unstable shifted to higher temperature as TKL wt% increases.
urethane bond from hard segment, but also the cleav- PU-CO presented the Tg at 0.76 C and is mainly
age of unstable ether linkages of lignin (Figure 7a, related to soft segments [19]. Increasing lignin con-
7c and 7e) [23]. Derivative curves for PU-CO/L20, tent shifted the Tg to a maximum value of 47.5 C for
PU-CO/L30 and PU-MCO1/L30 revealed two de- PU-CO/L30, mainly due to lignin rigid segment
composition peaks, as can be seen in Figure 7b and movements [19]. Lignin mass percentage and Tg shift-
7d. The two first stages, hard and soft segment degra- ing presented a linear dependence. Lignin mass frac-
dations, became close resulting in one larger peak, tion increasing also induced the tan peak broaden-
also observed by Zhang et al. [23]. The larger peaks ing, which implies in the sample heterogeneity and
have shifted to lower temperature and smaller inten- might be related to augment of molecular weight of
sity, compared to the second step decomposition of polyol component [36]. In this study, it might have
lignin free polyurethane, at 300400 C range. Lignin been induced by high molecular weight and hetero-
incorporation did not significantly affect the degra- geneous molecular structure of TKL added.
dation behavior but it rather increased the amount of Tan curves of PU-MCO1 and PU-MCO2 based
char formation, observed in TGA curves above polyurethanes are presented in Figures 8b and 8c. As
500 C. It was found that the char residue of lignin- general tendency, the Tg shifted to higher tempera-
containing polyurethanes increases as the lignin con- tures as TKL content increased. It can be seen in Fig-
centration increases. Table 2 presents additional ther- ures 8a, 8b and 8c that all lignin-containing polyure-

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Figure 8. DMA curves (tan ) of (a) PU-CO/lignin, (b) PU-MCO1/lignin and (c) PU-MCO2/lignin

thanes show a single tan peak, which is an indica-
tive of polyol components miscibility. PU-CO is the
only condition that presented a small secondary peak,
which might be associated to a slight phase separa-
tion between soft and hard segments in this compo-
sition.
It is of interest to evaluate the effects of CO modifi-
cation and TKL addition on polyurethane crosslink-
ing density (), which can be calculated using stor-
age modulus at rubbery plateau [36]. The crosslink-
ing density can be obtained, for samples submitted
to normal stress (tensile and flexural operation mode),
Equation (1) [37]:
ERl
o = 3RT (1)
where R is the gas constant, ER is the storage mod-
ulus at rubbery plateau and T the absolute tempera-
ture. Storage modulus at rubbery plateau and calcu-
lated crosslinking density are presented in Table 3.
Castor oil modification increased polyurethane cross-
linking density from 293 molm3 (PU-CO) to

Table 3. Storage modulus at rubbery plateau and crosslinking density of PU-CO/lignin, PU-MCO1/lignin and PU-
MCO2/lignin
PU-CO PU-CO/L10 PU-CO/L20 PU-CO/L30
ER [MPa] 2.5 6.1 6.9 13.2
[ molm3] 293 670 731 1360
PU-MCO1 PU-MCO1/L10 PU-MCO1/L20 PU-MCO1/L30
ER [MPa] 3.2 13.4 19.1 22.4
[ molm3] 331 1365 1919 2209
PU-MCO2 PU-MCO2/L10 PU-MCO2/L20 PU-MCO2/L30
ER [MPa] 5.4 9.1 13.1 14.6
[ molm3] 560 918 1288 1407

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560 molm3 (PU-MCO2). The crosslinking density
increasing of PU-CO/lignin, PU-MCO1/lignin and
PU-MCO2/lignin is a direct response of TKL wt%
rising. However, PU-MCO1/lignin presented higher
crosslinking density than PU-MCO2/lignin, besides
the higher crosslinking density value for PU-MCO2
in comparison to PU-MCO1.
3.4. Scanning electron microscopy (SEM)
Lignin-containing PU-COs presented a smooth tran-
sition from a ductile fracture (smooth grooves, white
arrows) to a brittle one (sharp surfaces, black arrows)
[38] near the TKL concentration value of 30 wt%,
as illustrate in Figure 9a and 9b; for the PU-MCO1,
there is a change in fracture mechanism at 20 wt%

Figure 9. SEM images of the fractured surface of the lignopolyurethanes with magnification of 10 000 (a, b and c) and
5000 (d, e and f)

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 Tavares et al. eXPRESS Polymer Letters Vol.10, No.11 (2016) 927940
TKL content (Figure 9c and 9d). This behavior is sim-
ilar for PU-MCO2, where the value is 10 wt% lignin
content (Figure 9e and 9f). It reveals that for PU-
MCO1 and PU-MCO2 this behavior is anticipated
due to lower lignin content.
3.5. Mechanical properties
Figure 10 summarizes the mechanical behavior of
the polyurethanes. First, the increased hydroxyl index
from CO to MCO1 and MCO2 substantially in-
creased the ultimate tensile stress (Figure 10a) and
the Young modulus (Figure 10c) of PU-MCO1 and
PU-MCO2 versus PU-CO. Polyurethane mechanical
behavior is mainly determined by the crosslinking
density given by the functionality of its reactants and
the stoichiometry between them [11, 39].
Figures 10b and 10d allow analyzing the effects of in-
creasing hydroxyl index on strain. Higher hydroxyl
indices decreased elastic strain (Figure 10d), which
might be associated to higher amounts of rigid seg-
ments and higher crosslinking density in the polymer
structure [11, 24]. Comparison of Figure 10b and
10d highlights the presence of plastic deformation
in PU-CO, PU-MCO1 and PU-MCO2 before rup-
ture. Considering that plastic deformation of ther-
Figure 10. Mechanical results of samples with different amounts of lignin: (a) ultimate stress, (b) ultimate strain, (c) Young
modulus and (d) elastic strain
937
mosets starts after chain scission and is not governed
by the crosslinking density [40, 41], a comparison
of the increasing hydroxyl index and the ultimate
strain is not feasible.
The introduction of TKL in the polyol strongly af-
fected the mechanical behavior and increases the ul-
timate tensile stress (Figure 10a) and Youngs mod-
ulus (Figure 10c) of lignin-containing polyurethanes.
The maximum tensile stress was 23.50 MPa, and the
maximum Youngs modulus was 2.00 GPa for PU-
MCO2/L30. The hardening effect caused by intro-
duction of TKL might be elucidated by two mecha-
nisms: i) Besides its participation as a co-monomer,
lignin has a reinforcement role derived from its char-
acteristics (aromatic rigid structure and Youngs mod-
ulus between 2.314.65 GPa) [20, 39, 42, 43];
ii) Crosslinking density increasing [11, 20, 44].
The ultimate strain for PU-CO and PU-MCO1 in-
creased by adding TKL up to 20 and 10 wt%, respec-
tively. As TKL weight contents rises for these com-
positions, the ultimate strain decreases. This ultimate
strain trend inversion converges to ductile-to-brittle
transition, as shown in Figure 9, and is related to more
rigid segments and consequently to glass transition
temperature shifting. The ductile-to-brittle transition
 Tavares et al. eXPRESS Polymer Letters Vol.10, No.11 (2016) 927940
occurred around 45 C for lignin-containing poly-
urethanes, based on CO or MCOs, as can be observed
in DMA results.
Results pointed out that the mechanical properties of
lignin-containing polyurethane are in agreement with
the mechanical properties of petroleum based poly-
urethanes, such as polyurethane adhesives (Young
modulus: 0.73 to 2.25 MPa; ultimate tensile stress:
17.84 to 40.03 MPa) [45, 46] and crosslinked poly-
urethanes (typical ultimate tensile stress: 1.70 to
41.00 MPa) [4749]. PU-MCO2/L30 presented the
highest Young modulus in comparison with recent
published results concerning 100% bio-based poly-
ols based polyurethanes [23, 50, 51].
4. Conclusions
Polyurethanes based on renewable raw materials
(technical Kraft lignin, castor oil and modified castor
oil) were prepared. The results indicated that the start-
ing materials change the polymers properties. The
oil modification process improved hydroxyl concen-
tration and lead to polyurethanes with enhanced me-
chanical properties versus ones synthesized from un-
modified castor oil. The introduction of TKL in-
creased the glass transition temperature of the mate-
rials from 0.76 C for PU-CO to 47.5 C for PU-
CO/L30 and had a twofold effect on the mechanical
properties. The reinforcement co-monomer and fur-
ther increase in hydroxyl content led to a higher
crosslinking density. The products show the feasibil-
ity of developing polyurethane-type materials with
large property range, by using an industrial low cost,
unmodified and largely available residue combined
with no edible renewable source oil.
Acknowledgements
The authors thank FAPESP/CNPq and acknowledge UFABC
(Federal University of ABC) for the doctoral fellowship of
L.T. and A.N., the master fellowship of C.B. and G.S. and
nancial support.
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